The electrochemically-assisted synthesis of (hetero)arylphosphonates from (hetero)aryl halides and dimethyl phosphite is described. Very mild and simple conditions are employed as the cross-coupling is carried out in galvanostatic mode, in an undivided cell at room temperature, using NiBr₂bpy as the easily available pre-catalyst and acetonitrile as the solvent. In addition, both aryl bromides and iodides can be used as well, providing the corresponding (hetero)arylphosphonates in generally good yields. A mechanism involving the in situ generation of a Ni ate complex is proposed.

A range of novel 4-amino-6-arylpyrimidines has been prepared under mild conditions by an electrochemical reductive cross-coupling between 4-amino-6-chloro-pyrimidines and functionalized aryl halides. The process, which employs a sacrificial iron anode in conjunction with a nickel(II) catalyst, allows the formation of coupling products in moderate to high yields.